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Sequence of Structural and Magnetic Phase Transitions in (NO)Mn<sub>6</sub>(NO<sub>3</sub>)<sub>13</sub>
New nitrosonium manganese(II) nitrate, (NO)Mn6(NO3)13, has been synthesized and structurally
characterized.
In the temperature range of 45–298 K, the crystal is hexagonal
(centrosymmetric sp. gr. P63/m). Mn2+ ions are assembled into tubes along axis c with both NO3– filling and
coating. The nitrosonium cation is located in the framework cavity
and is disordered by a 3-fold axis. At the temperature TS1 = 190 K, a structural phase transition related to the
libration of the intertube NO3 group and a small variation
of Mn polyhedron is observed. Moreover, the anomalies in physical
properties of (NO)Mn6(NO3)13 allow
suggesting that ordering of NO+ units occurs at low temperatures.
The antiferromagnetic ordering in this compound is preceded by the
formation of a short-range correlation regime at about 25 K and takes
place in two steps at TN1 = 12.0 K and TN2 = 8.4 K